Polymeric composition comprising sulfonyl carbazates as blowing agents

ABSTRACT

Sulfonyl carbazates containing at least one group of: -SO2-NHNHCOOwherein the oxygen and the sulfur atoms attach to various organic groups are useful as high temperature blowing agents for gas-expandable polymers. Additionally, novel polyfunctional and secondary-alkyl substituted sulfonyl carbazates have been discovered.

United States Patent [1 1 1 3,925,270

Hunter Dec. 9, 1975 POLYMERIC COMPOSITION COMPRISING [58] Field ofSearch 260/25 R, 2.5 HA, 2.5 HB.

SULFONYL CARBAZATES AS BLOWING AGENTS Inventor: Byron A. Hunter,Woodbridge,

Conn.

Assignee: Uniroyal, Inc., New York, NY.

Filed: June 5, 1974 Appl. No: 476,752

US. Cl 260/25 R; 106/122; 260/25 D; 260/25 N; 260/25 HA; 260/2.5 l-l;260/25 HB; 260/25 P; 260/25 FP; 260/3; 260/13; 260/285 D; 260/4247;260/4248;

260/4252; 260/793 M; 260/470; 260/47] R, 260/480; 260/48] R; 260/724;260/823; 260/857 R; 260/860; 260/874; 260/887; 260/898; 260/899; 260/900Int. Cl. C08J 9/06 260/470, 471 R. 480, 481 R, 793 M {56] ReferencesCited UNITED STATES PATENTS 3,235,5[9 2/1966 Hunter 260/25 R PrimaryExaminer-Morton Foelak Attorney, Agent. or Firm-Bruce E. Jacobs, Esq.

19 Claims, N0 Drawings 1 POLYMERIC COMPOSITION COMPRISING SULFONYLCARBAZATES AS BLOWING AGENTS BACKGROUND OF THE INVENTION chemicalblowing agents in the expansion of polymers. 1

The chemicals of the invention are particularly valu able in theexpansion of polymers such as elastomers and plastics which are normallyprocessed at elevated temperatures and especially in plastics which areprocessed at temperatures above 225C. Particular chemicals herein areeven useful at expansion temperatures in excess of 250C.

The sulfonyl carbazate compounds of this invention contain at least onechemical group of -SO2NHNHC00- wherein the oxygen and the sulfur eachattach to a various organic group, as hereafter described.

DESCRIPTION OF THE PRIOR ART The use of certain monofunctional arylsulfonyl carbazates of the structure K so -NHNH.COQ.C H

where X is H, CH OCH CH CO--NH, Cl, Br, or N in medicinal preparations,as wetting and lubricating agents, in the textile industry, in the dyeindustry, as herbicides, and as sedatives has been known from sucharticles as Zhurnal Organicheskoi Khimii, Vol. 7, No. 4, pp. 794-798,April l97l, J. Chemical Society (c) 1970 (org) 2629, and Current ScienceNo. II, 1966, p. 283-4. However, none of these references has anysuggestion of the usefulness of these compounds as blowing agents, noris there any suggestion or disclosure of polyfunctional orsecondary-alkyl substituted sulfonyl carbazates, the new compounds ofthis invention.

Blowing agents which decompose at relatively high temperatures are notnew. US. Pat. No. 3,235,519 discloses using sulfonyl semicarbazides asblowing agents for polymeric materials which soften above 170C. Theseblowing agents are particularly suitable for expanding high densitypolyethylenes, and many other rubbery and plastic polymers, but they areunsuitable for expanding certain polymers because they produce ammoniagas upon decomposition, which tends to attack some polymeric materialssuch as polycarbonates and polyesters, and, in some instances, to reactwith the metals used for the construction of molding equipment.

SUMMARY OF THE INVENTION This invention provides a new class of blowingagents which decompose non-explosively, and controllably at temperaturessuch as to be valuable in the expansion of polymers such as elastomersand plastics which are normally processed at elevated temperatures andespecially in plastics which are processed at temperatures above 225C.Particular chemicals of the invention are useful at expansiontemperatures in excess of 250C.

The invention also provides novel polyfunctional and secondary-alkylsubstututed sulfonyl carbazates. The secondary-alkyl substitutedsulfonyl carbazates either monoor polyfunctional are particularlypreferred because of their unexpected high gas evolution efficiency whencompared with similar primary alkyl-substituted compounds.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The sulfonyl carbazatecompounds of this invention contain at least one SO -NHNI-ICOO group permolecule, wherein the oxygen and sulfur are each bonded to variousorganic groups, as shown below.

There are four basic structures which the sulfonyl carbazates of thisinvention may possess.

First, the oxygen may be attached to a monofunctional group and thesulfur to another monofunctional group so as to give a structure ofR-so,-NHNH coo-R' I wherein R and R are the same or different and may bealkyl or alkenyl radicals having I to l2 carbon atoms; aryl, aralkyl,and alkaryl radicals containing 6 to 10 carbon atoms; and cycloalkylradicals containing 5 to 8 carbon atoms, especially cyclohexyl. Theseradicals may be substituted by halogen or hydroxy groups.

Secondly the oxygen may be attached to a monovalent group as in FormulaI while the sulfur is attached to a divalent group resulting incompounds of the structural formula wherein both R radicals may be thesame or different, preferably the same, and have the same meanings asindicated above. Y is a divalent radical such as alkylene having 2 to 12carbon atoms, arylene or alkarylene having 6 to 12 carbon atoms, or agroup of the structure wherein Z is a single bond connecting R and R oris --O, -S, SO, SO -NR"- wherein R is hydrogen or an alkyl group havingfrom I to 4 carbon atoms, or Z is an alkylene radical having from I to 6carbon atoms such as methylene, ethylene, propylene, tetramethylene andhexamethylene, or an alkylidene radical having 2 to 3 carbon atoms suchas ethylidene and isopropylidene and R and R may be the same ordifferent and are alkylene having 2 to 4 carbon atoms and phenylene.

Thirdly, the sulfur is attached to a monovalent group and the oxygen isattached to a divalent group leading to compounds of the structuralformula III wherein the two R groups may be the same or different,preferably the same, and have the same meanings as indicated above, andY has the same meaning as Y above.

And fourthly, both the oxygen and the sulfur may be attached to divalentgroups thereby producing a polymer of the structure wherein Y and Y asdefined above and n is an integer from 2 to I00, preferably 2 to 50.

It can thus be seen that sulfonyl carbazate blowing agents may bedescribed as hydrazine derivatives in which a hydrogen atom on onenitrogen atom is substituted by an organic sulfonyl radical and onehydrogen on the other nitrogen atom of the hydrazine moiety issubstituted by a carbohydrocarboxy group. Thus, using this system ofnaming compounds, the following are illustrative both of names ofcompounds and of blowing agents useful for the purposes of theinvention, especially those represented by Formula I above:

N-Benzene sulfonyl-N'-carbomethoxy hydrazine N-Benzenesulfonyl-N-carboethoxy hydrazine N-Benzene sulfonyl-N-earbo-n-propoxyhydrazine N-Benzene sulfonyl-N'-carbiosopropoxy hydrazine N-Benzenesulfonyl-N'-carbobutoxy hydrazine N-Benzene sulfonyl-N-carboisobutoxyhydrazine N-Benzene sulfonyl-N-carbo-sec-butxy hydrazine N-Benzenesulfonyl-N'-carbo-tert-butoxy hydrazine N-Benzenesulfonyl-N'-carbo-2-methyl-2-butoxy hydrazine N-Benzenesulfonyl-N'-carbo-3-methyl-2-butoxy hydrazine N-Benzenesulfonyl-N-carbo-3,3-dimethyl-2-butoxy hydrazine N-Benzenesulfonyl-N-carbo-3-methyl-2-pentoxy hydrazine N-Benzenesulfonyl-N'-carbo-4-methyl-2-pentoxy hydrazinesulfonyl-N'-carbo-2-methyl-2-butoxy The compounds and blowing agentswhich correspond to Formula II are exemplified by the following, whichmay be termed sulfonyl hydrazides:

l,3-Benzenebis( 3-carbomethoxy sulfonyl hydrazide)1,3-Benzenebis(3-carboethoxy sulfonyl hydrazide)l,3-Benzenebis(3-carbo-n-propoxy sulfonyl hydrazide) l ,3-Benzenebis(3-carboisopropoxy hydrazide) l,3-Benzenebis( 3-carbobutoxy sulfonylhydrazide) 1,3-Benzenebis(3-carbo-sec-butoxy sulfonyl hydrazide)l,3-Benzenebis(3-carbo-tert-butoxy sulfonyl hydrazide)Toluene-2,4-bis(3-carbomethoxy sulfonyl hydrazide)T0luene-2,4-bis(3-carb0is0propoxy sulfonyl hydrazide) Toluene-2,4-bis(3-carbo-tert-butoxy sulfonyl hydrazide)meta-Xylene-4,6-bis(3-carbomethoxy sulfonyl hy drazide)meta-Xylene-4,6-bis(3-carboethoxy sulfonyl hydrazide)meta-Xylene-4,6-bis( 3-carboisopropoxy sulfonyl hydrazide)meta-Xylene-4,6-bis( 3-carbo-tert-butoxy hydrazide) 4,4'-Biphenylenebis(3-carbomethoxy sulfonyl hydrazide) 4,4'-Biphenylenebis(3-carboethoxysulfonyl hydrazide) 4,4'-Biphenylenebis(3-carboisoporpoxy sulfonylhydrazide) 4,4'-Biphenylenebis( S-carbo-sec-butoxy sulfonyl hydrazide)4.4-Biphenylenebis(3-carbo-tert-butoxy sulfonyl hydrazide)Napthalene-l,5-bis(3-carboisopropoxy sulfonyl hydrazide) Naphthalene-1,5-bis( 3-carboallyloxy sulfonyl hydrazide) Naphthalene-l,5-bis(3-carbooctoxy sulfonyl hydrazide) Ethane-l,2-bis(3-carboethoxy sulfonylhydrazide) Ethane-l,2-bis(3-carbo-sec-butoxy sulfonyl hydrazide) Ethane-1 ,2-bis( B-carbo-tert-butoxy sulfonyl hydrazide) Propanel ,2-bis(3-carboisopropoxy sulfonyl hydrazide) Butane-1,4-bis(B-carbo-tert-butoxysulfonyl hydrazide) Butanel ,4-bis( 3-carbo-4,4-dimcthyl-2-hexoxy sulfonyl hydrazide) Butane l ,4-bis( 3-carbo-4-ethyl-2-hexoxy hydrazide)Butane l ,4-bis( 3-carbododecyloxy sulfonyl hydrazide) p,p"Diphenyletherbis(3-carbomethoxy sulfonyl hydrazide) p,p'-Diphenyletherbis(3-carboethoxy sulfonyl hydrazide) p,p'-Diphenyletherbis(3-carboisopropoxy sulfonyl hydrazide) p,p-Diphenyletherbis(3-carbo-n-propoxy sulfonyl hydrazide) p,p'-Diphenyletherbis(3-carbo-sec-butoxy sulfonyl hydrazide) sulfonyl sulfonyl Thecompounds and blowing agents which correspond to Formula Ill areexemplified by the following, which may be termed sulfonyl carbazates:

l,2-Ethylenebis( 3-benzene sulfonyl carbazate) l ,2-Ethylenebis(3-p-toluene sulfonyl carbazate) l,5-Oxydiethylenebis(3-p-toluenesulfonyl carbazate) l,5-Oxydiethylenebis( 3-benzene sulfonyl carbazate)l,2-Ethylenebis( 3-methane sulfonyl carbazate) l,5-Oxydiethylenebis(3-propane sulfonyl carbazate) 4,4-Biphenylenebis( 3-methane sulfonylcarbazate) p,p-Oxydiphenylenebis(3-benzene sulfonyl carbazate)p-Phenylenebis( 3-butane sulfonyl carbazate) The sulfonyl carbazatecompounds of this invention can be prepared by either of two generalprocedures. One method (I) is to react a sulfonyl hydrazide with achloroformic ester essentially in a l to 1 molar ratio and generally ina solvent or suspending medium and in the presence of a base to removethe acid formed. The reaction is:

The other method (II) is to react an organic sulfonyl chloride with anester of carbazic acid, again generally in a solvent or suspendingmedium and in the presence of a base, according to the reaction:

The R and R'being any of the groups defined above, and as illustrated inthe examples below. The solvents or suspending medium for either methodmay be such as water, methanol ethanol, tetrahydrofuran,dimethylformamide, acetonitrile, isopropanol, ethylene dichloride andtrichloroethyene.

The polymeric materials which may be expanded by these blowing agentsinclude homopolymers, interpolymers, graft polymers, and mixtures andblends of two or more of these, and include thermoplastic,thermosetting, and rubbery polymers. In particular, the new blowingagents are useful for expading polymers that have high processingtemperatures such as the polycarbonates, phenylene oxide-based resins,polyaryl sulfones, the various nylons, polyesters, certain polystyrenes,polypropylene, poly(styrene-acrylonitrile), polyacetals, poly(vinylchloride), poly(vinyl acetate), polyphenylene sulfide,poly(methylpentene), low and high density polyethylenes, polyimides,polyaryl ethers, ABS polymers, polyacrylics, cellulosic polymers,halogenated polymers, especially the fluoroplastics, poly-(ethylene-vinyl acetate), and polymer alloys. Other polymers includepoly(butadiene-styrene), polyisoprene (including natural rubber), cisortranspolybutadiene, butyl rubber, ethylene-propylene copolymers,ethylene-propylenenon-conjugated diene terpolymers, andpoly(butadiene-acrylontrile).

Generally, the amount of blowing agent used will depend on the nature ofthe polymer to be expanded, and the desired density of the foam to beproduced. Usually, 0.05 to l5, and most often, 0.2 to 5.0 parts ofblowing agent are employed, based on I00 parts of polymer by weight. Theblowing agents can be used alone, or in combination with other blowingagents. Activating substances can be used to increase the efficiency ofgas evolution, or to lower the normal decomposition temperature, of theblowing agents of the invention. Other additives such as plasticizers,fillers, nucleating agents, and the like can also be added to thepolymer to be expanded.

Particularly effective blowing agents are those sulfonyl carbazatescontaining a secondary alkyl substituent on the oxygen atom of thecarboxy group. The secondary alkyl substituted compounds show greatlyincreased gas evolution as compared to the primary alkyl containingrelated compounds. In particular, the isopropoxy derivatives generallyyielded 35 to more gas than the n-propoxy comparable derivative.

The following examples illustrate the preparation of some of thesulfonyl carbazates of the invention, their efficiency as gas-producingagents upon decomposition, and their use as blowing agents for producingexpanded polymeric materials.

EXAMPLE I .N-METHANESULFONYL-N'-CARBOlSO- PROPOXY HYDRAZINE ln a l-liter3-neck flask is placed 17 g (0.5 mole) anhydrous hydrazine, 27 g. (1/4mole) Na CO and I00 cc. acetonitrile. The mixture is stirred as 57.3 g.1/2 mole) of methanesulfonyl chloride is added slowly. The temperatureof the mixture increases and CO is evolved. Then another 27g. of l} la-CO; is added to the mixture and the mixture is stirred as 61.5 g. (0.5mole) of isopropyl chloroformate is added, keeping the temperature under40C. Finally the mixture is stirred 2 hours and then cooled to 10C. andfiltered, washed with cold water and dried. This product melts atl29-l3lC.

Analysis: %N calc. I42; found l3.84. %S calc. l6.3; found l6.08. %Ccalc. 30.6; found 30.8l. %H calc. 614; found 6.54.

EXAMPLE ll N BEN ZENESULFONY L-N -CARBOMETHOXY HYDRAZINE %N calc. 12.2%;found l2. l6%.

Analysis:

%5 calc. 13.9%; found l4.19%.

EXAMPLE III N-BEN ZENESU LFONY L-N BETA-HYDROXY CARBOETHOXY) HYDRAZINETo 60 g. of hydroxyethyl carbazate are added l00 ml. water and 42 g.Nal-lCO The mix is Stirred and 88-25 Analysis: %N calc. 10.76%; found10.95%. %S calc. 12.3%; found 12.56%.

EXAMPLE 1V N-BENZENESULFONYL-N'-(CARBO1SOPRO- POXY) HYDRAZlNE A mixtureof 172 g. (1.0 mole) of benzenesulfonyl hydrazide, 100 g. NaHCO 200 ml.ethanol and 25 ml. water is stirred as 128.6 g. (1.05 mole) of isopropylchloroformate is added dropwise over 15 minutes. The temperature risesfrom 25 to 44C. as CO is evolved during the addition. The mix is stirredfor two hours more and the temperature rises as high as 53C. (10minutes) and then drops. Then 1000 ml. of water is added over a tenminute period. The mixture is stirred an additional hour and is thencooled to 15c. The white crystalline product is filtered off and washedfirst with water and then with hexane. The dried product weighs 234.5 g.This crude product melts at 83-127C. and decomposes when heated over220C.

The material is dissolved in ammonium hydroxide, the aqueous solutionbeing extracted with ether. The aqueous layer is then acidified and thewhite crystalline product filtered off and washed with water and dried.112 g. of product are recovered which melt at 88247C.

Analysis: %N calc. 1085; found 10.75.

%S calc. 12.40; found 12.49.

EXAMPLE V N-BE NZEN ESULFONY L-N '-CARBOALLYLOXY HYDRAZlNE Analysis: %Ncalc. 1 1.3%; found 1 1.46%.

%S calc. 12.5%; found 12.41%.

EXAMPLE Vl N-BENZENESULFONYL-N'-CARBOPHENOXY HYDRAZINE [n a literreaction flask is placed the following:

34.4 g. (0.2 mole) Benzenesulfonyl hydrazide 200 ml. water 20 g. NaHCO31.3 g. (0.2 mole of phenyl chloroformate are added with stirring. Themixture is the stirred for four hours and the crystalline productfiltered off, washed and dried. Yield 52.0 g. This melts at 45 C. Afterrecrystallization from ethanol the material melts at 15lC.

Analysis: %N calc. 9.58; found 9.64%. %S calc. 10.96; found 11.29%.

EXAMPLE Vll N-(P-TOLUENESULFONYL)-N'-(CARBOETHOX- Y)HYDRAZINE Analysis:%N calc. 10.80%; found 1 1.07%. %S calc. 124%; found 12.68%.

EXAMPLE V111 N-P-TOLUEN ESULFONYL-N '-1SOPROPOXY HYDRAZINE A mixture of186 g. 1.0 mole) p-toluene sulfonyl hydrazide, 100 g. Nal-lCO 200 m1.ethanol and 25 ml. of water is stirred as 128.5 g. (1.05 mole) isopropylchloroformate is dropped in. The temperature gradually rises to 43C. Oncontinued stirring the mixture gradually changes to a crystalline mush.1600 ml. of water is added and the mixture is stirred ten minutes. Theproduct is filtered off and washed well with water and dried. Yield 231g. This product is taken up in concentrated ammonium hydroxide andfiltered from some insolubles. Treatment with water and dilutehydrochloric acid precipitates a product, which, after washing withwater and drying (60C) weighs 154 g. and melts at 1 1.5112C. A portionis recrystallized from ethanol and melts at 112-1l3C.

%N calc. 10.30; found 10.37. %S calc. 11.75; found 13.54.

Analysis:

EXAMPLE 1X 5 the gas evolution date in Table 1B the compounds con- 9 Thegas evolution is measured by heating the compound beyond itsdecomposition point in contact with TABLE l-continued a heat transfermedium, such as a silicone oil. and the o B Ewlulm Run N11. m.p. C cc/gcc/mmole volume of gas evolved 1s determined by difference 1n a mercuryfilled gas hurette. The final volume of the ex- 5 2 53 22-8 panded gasis taken at room temperature and then cori 1,3 bj 5 rected to standardtemperature and pressure. 29 I374" 159 TABLE I Run Method R' AnalysisNo. 91c 91.11 04 N %s 91 c1 1 11 (11., CH.. 212312142) 4.791476)164311667) 11111411905) 2 11 (1,11 262012637 571115511 15211115311)11109117511 3 1 c 11. 30111 31161 6.101612) 139011429) l6.33[ 16.33) 411 1cm, 30111131161 6.3111612 139411429) 111.0111 16.33) 11 10.11,,34.351.34.29 67316.67 131111333) 157611524) 5 6 11 2-c,11,, 34.13 6.6413.13 15.34 7 11 11 C11 262112637 541115.50) 1490115311) 1721117511) 1111 C2H 31111113061) 6.301612) 1311411429) l6.3l(16.33) 9 11 11-0 11,33.931.34.29) 6.87(6.67) 1311211333) 15111111524) 111 11 141.11, 33.926. 13.011 15.22 11 11 20.11,, 370113750) 72717.14) 1235 1250) 142511429)12 11 "-0.11. (211 3371113429) 6671667 1304 1333 1511111524) 13 11143.11, 4002141134 7.6111756) 11.521 1 1.76) 133511345) 14 11 11-0131,39.73 7.69 11.55 13.211

16 11 c 11,, (4426) 14.92 111.411) (13.11) 17 11 n-( =,H, 46.37(46.5 1)5.331542 1070110115 122011240) m n its? 19 1 n-c,1-1 48.S6(48.53)6.1215119 102111029) 1 1.5211176 20 11 i-C,H,, 411.32 5.114 10.17 11.5521 11 2-0111. 48.64 5.93 10.13 11.57 22 1 1143. 11 5117715937 115011133)7.011 729 8.1411133 23 1 Q- C11a 4392144211) 511014.92) 1110111421129711311) 24 1 C,1-1 (46.51) 15.42 1 1.0711035) l2.68( 12.40 25 11|1-C.,H 48.2l(48.53) 5.9115419 1030 1029 1 177 11.76

29 11 0Q- 011 3613136311 3.161340) 10.11106) 12.11121) 13.611134) 30 11C-,H, 39.121387 4.06 396 9.67(l0.8) 11.541115) 13.24 127 31 11 1 n-C H40.91410 4.431445 11.971955 10.11 41 10.9) l2.68( 12.1 32 11 i-C H,40.71 4.48 9.20 10.86 13.311 33 11 2-c.11 43.251431 4.92 491) 8.83(9.l8)l0.36( 10.42) 12.04 1 1.6)

34 11 9-04 n-C H 41164 4116) 6.0615118 101911029 11.66 1 1.76)

35 11 i-C H 48.56 5.90 10.11 11.711

30 137-1311 145 40.4 TABLE I 31 107-1011 144 42.1

B Gas Evolution R .C 1 1 un Nu m p tc/g cc/mmo e 34 "402 I21 329 1105-106 303 50.9 35 134-135 I85 503 2 39.5-90.5 286 52.2 3 1055-1065 21942.9 4 129-131 330 64.7 5 1055-106 231 411.5 6* 111-112 314 65.9 EXAMPLEX Z 2-45 g BUTANE- l ,4-BlS( 3-CARBO-N-PROPOXY 1, 3 1 1 SULFONYLHYDRAZIDE 10 137-139 305 63.6 H 275 M6 Into a ll1ter 3-neck flask isplaced 25.5 g. (0.l mole) 12 67 352 61) butane-l,4-disulfonyl chloride,200 ml. methanol and :3 3: 1 20.0 g. (0.24 mole) of NaHCO; With stirring26.0 g. 15 149-150 1112 41.9 (0.22 mole) of n-propyl carbazate is added.lt is heated :3 5: 3 :2; 33-1, to reflux with stirring for two hours,cooled and diluted 83414 2211; :1 with 300 ml. water, stirred until asolid separates. The l3 {ii- I! 74 ,5 solid is filtered and taken up inconcentrated ammo- 5. 55: g nium hydroxide solution. It is filtered andthe filtrate is 22 79-1111 acidified with dilute sulfuric acid. Theseparated solid is 33 filtered off and washed with water. The driedroduct 24 105-1055 171 44.1 o o p 25 -7h 149 40.5 weighs 20.5 g. m.p.163 5 C.

This product produces a large volume of gas when heated above 260C. (161cc/g STP) 1.3-D1METHYLBENZEN E-4,6-BlS(3-CARBO- METHOXY SULFONYLHYDRAZIDE A l-liter reaction flask is charged with 60.6 g. (0.2 mole)l,3-dimethylbenzene-4,6-disulfonyl chloride, 32 g. (0.4 mole) pyridineand 300 ml. ethylene dichloride. The mixture is stirred as 36 g. (0.4mole of methyl carbazate in 100 ml. ethylene dichloride at a temperatureof about 50C. is added over 30 minutes. The temperature rises to 55C.The mixture is then stirred and heated to gentle reflux for 1/2 hour.150 ml. of water is added and the mixture is cooled to C. The whiteprecipitate is filtered off and washed well with water. The driedproduct weighs 50 g. and melts with decomposition at 237 C. The productis then dissolved in ammonium hydroxide solution, filtered and thefiltrate acidified with dilute sulfuric acid. There is recovered 44 g.(dry) of product which melts with decomposition at 240C.

%N calc. [3.66; found 13.40. %S calc. 15.61; found 1538.

Analysis:

A 2-liter reaction flask is charged with 60.6 g. (0.2 mole) ofl,3-dimethylbenzene-4,6-bisulfonyl chloride, 32 g. (0.4 mole) ofpyridine and 500 ml. of ethylene dichloride. The mixture is stirred as41.6 g. (0.4 mole) of ethyl carbazate is added dripwise over l/2 hour.The temperature rises from C. to 50C. The mixture is heated to gentlereflux for 1/2 hour and then cooled to 20C. The ethylene dichloridelayer is removed and the oily lower layer, when placed in water, becomescrystalline. The white product is filtered off and then dissolved inammonium hydroxide solution. The filtered solution is acidified withdilute sulfuric acid and the resulting precipitate filtered off, washedwell with water and dried. Yield 57 g.; m.p. l88-190C. (dec. 200-260C.

%N calc. 12.78; found 12.38. 705 calc. 14.61; found 14.53.

Analysis:

12 mp. 148-l52C. Decomposition Range l265C.

Analysis: %N calc. 12.07; found 1 1.67.

%S calc. 1373; found 13.52.

EXAMPLE XIV NAPHTHALEN E-l ,5-BlS(3-CARBOET1-[OXY SULFONYL HYDRAZIDE)lnto a l-liter 3 neck flask is placed 32.5 g. (0.1 mole)napthalene-l,5-disulfonyl chloride, 180 g. (0.2 mole) sodium,bicarbonate and 200 ml. methanol. Then 20.8 g. of ethyl carbazate isadded and the mixture is stirred and heated to gentle reflux for 2hours. The cooled product is filtered, washed with water, and dried.Yield 37.5 g. This material is then dissolved in 300 ml. of concentratedammonium hydroxide, filtered (through celite) and the filtrate isacidified with dilute sulfuric acid. The resulting solid is filtered,washed with water and dried. Yield 35.0 g. m.p. =265C. (dec.)

4,4 -B1PHENYLENEB1S( 3-CARBOMETHOXY SULFONYL HYDRAZIDE) In a 5-literflask is placed 342 g. (1.0 mole) of biphenyl-4,4-disulfonyl hydrazide,200 g. sodium bicarbonate (2.4 mole), l liter of acetonitrile and ml.water. The mix is stirred as 208 g. (2.2 mole) of methyl chloroformateis added slowly. The mix is then stirred for 3 hours at 40C. and thetemperature is gradually increased to reflux temperature (1 hour). Themix is cooled and the product is filtered, washed with water and dried.Yield 520 g.

Purification of a portion is performed by dissolving it in concentratedammonium hydroxide, filtering, and acidifying the filtrate. The whitesolid is filtered off, washed with water and dried. This melts withdecomposition at 24925 1C.

Analysis: Cale. found %C 42.0 42.50 %H 3.95 4.36 %N l 2.2 l 1.63 %S l3.95 13.92

EXAMPLE XVT 4,4'-B1PHENYLENEB1S( Z-CARBOETHOXY SULFONYL HYDRAZlDE) 70.2g. (0.2 mole) of 4,4'-biphenyldisulfonyl chloride, 400 ml. acetonitrileand 40.0 g. (0.47 mole) sodium bicarbonate are placed in a liter flask.The mix is Analysis: calc. found %C 44.5 44.89 %H 4.52 4.39 %N 1 1.50 l1.32 13.15 13.14

EXAMPLE XVII 4,4 -BlPHENY LENEBIS( 3-CARBO-N-PROPOXY SULFONYL HYDRAZIDE)A 2-liter flask is charged with 70.2 g. (0.2 mole) ofbiphenyl-4,4-disulfonyl chloride, 800 ml. ethylene dichloride and 32 g.(0.4 mole) pyridine. The temperature is adjusted to 55C. (completesolution) and the solution is stirred as 47.2 g. (0.4 mole) of n-propylcarbazate is added dropwise over 1/2 hour, keeping the temperaturebetween 55-60C. The mix is stirred an additional hour and is cooled to20C. The ethylene dichloride layer is pured off and the semicrystallineresidue is mixed with water. The crystalline product is filtered off,washed with water and dried at 60C. Yield 100 g. (97% of theory). m.p.152-158C, dec. 195260C.

4,4'-BlPl-IENYLENEBIS( 3-CARBO-2-ETHYLHEX- OXY SULFONYL HYDRAZIDE) A3-liter flask is charged with 171 g. (0.5 mole) ofbiphenyl-4,4-disulfonyl hydrazide, 92.4 g. (1.1 mole) of sodiumbicarbonate and 500 ml. acetonitrile. The mix is stirred as 202.1 g.(1.05 mole) of 2-ethylhexy1 chloroformate is poured in. The mix isheated gradually to 60C. and CO is evolved. After 56 hour the mixbecomes quite thick and 500 m1. of acetonitrite is added. The mixture isrefluxed for two hours and is then cooled and filtered. About 37 g. ofinsoluble material is removed. Two liters of water is then added to theacetonitrite filtrate. A precipitate gradually fonns. After /a hour thisis filtered off, washed well with water and dried. Yield 184 g. Aportion is recrystallized from ethanal. m. p. 144146C.

-continued Analysis: calc. found %S l 0. l 9.9 1

EXAMPLE XlX DlPHENYL ETHERBIS (BENZENE-3-CARBOMETHOXY SULFONYLHYDRAZIDE) To a 3-liter flask are added 17.9 g. (0.5 mole) diphenyletherbis(benzene-sulfonyl hydrazide), g.

(1.13 mole) sodium bicarbonate and 500 mml. Methanol. With stirring 103g. (1.1 mole) of methyl chloroformate is gradually added. After all hasbeen added the mix is stirred for two hours. A liter of water is added,whereupon the product crystallizes. The white solid is filtered ofi',washed with water and dried. Yield 166 g. A portion is dissolved inconcentrated Nl-LOH, filtered and precipitated with acid and theresulting solid is recrystallized from ethanol, and it melts atl24-125C.

EXAMPLE XX DIPHENYL ETHERBIS (IS-CARBOETHOXY SULFONYL l-lYDRAZlDE) Amixture of 30 g. (0.004 mole) of diphenyl etherbis- (benzenesulfonylhydrazide), 50 ml. ethanol and 25 ml. water is stirred as 9.1 g. (0.042mole) of ethyl chloroformate is dropped in over k hour. Practically allpasses into solution. Then 14.1 g. (0.168 mole) of Nal-lCO is addedgradually, with C0 being evolved. Then a further 9.1 g. of ethylchloroformate is added slowly. The mix becomes cloudy and after twohours stirring a heavy precipitate forms. The mixture is diluted withcc. of water and the solid filtered off and washed with water and dried.A portion is recrystallized from ethanol. This melts at C. anddecomposes when heated to 2l0-240C.

Analysis: calc. 1 found A mixture of 179 g. (/2 mole) diphenyl etherbis(benzene sulfonyl hydrazide), 100 g. NaHCO 200 ml. water is stirred as128.6 g. (1.05 mole) of isopropyl chloroforrnate is added over a periodof 20 minutes as the temperature rises from 25 to 32C. Stirring iscontinued for two hours as the temperature increases to 40C. (after 1sthalf hour) and then drops off. 250 m1. of methanol is added to keep themixture stirrable. Then 1000 ml. of water is added over ten minutes andthe mixture is cooled to 10C. (ice water) and the prod- 16 uct isfiltered and washed well with hot water and dried. 1 16111 196 g. mp.1s9 191c. (dBQ). EXAMPLE The basic procedures of Examples X-XXI arerepeated for various compounds of the structure of For- Malysis: found 5mula [I wherein the Y and R radicals are as defined in 7N 10.57 10.74Table llA below. Table [1B gives the melting points and 2122 gasevolution data for these compounds.

TABLE ll A Run Method Y R Analysis ND. %C 9611 9m 71s 11 1,442.11. 121-1264126.52) 50614.97) 15.01 [5.46) l7.64( 17.68] 41 11 c 11 301813079)56715.64) 13.7911436) l6.46( 16.41 42 1 n-C H 34.19 34.45 633 672)132211340) 1431 1531 43 11 i-c n, 34.13 6.43 12.86 15.56 44 11 1-c.H.,37.02(37.67) 6.63(6.73] 11.771 12.56 14.581 14.35) 45 11 242.11,. 37.517.06 12.00 14.42

47 11 3 6 4s 11 n.c,1-1, 49 11 i-C H 50 11 243,11

52 11 c 11, 53 11 .1 54 11 i-C H 55 1| 2-0 11,

56 ll CH CH;,

57 11 c 11 58 11 n-C H 59 1 i-C,H, 409114120) 5.6015511 ll.S6( 12.01)13.621 13.73 60 1 2-c H,

1:11 64 1 1E 1-0 11, 409414120) 5.59(5.58) ll.64( 12.01 l3.64( 13.73

66 11 -Q CHa 67 11 cm, 68 11 n-C H, 412914120 5.761558) ll.6l(l2.0l)l3.38(l3.73) 69 11 i-C H 41.36 5.56 11.98 13.37 70 11 2-c.1-1 71 11 C1172 11 C,H 4l.64(4l.74) 4.l8(4.35] 11.70 12.17 134311391) 7:1 11 n-c,1-144.29(44.26) 4.37 492) 10119111411 l2.84( 13.1 1) 74 11 i-C H, 44.065.00 11.14 13.10 75 11 i-C.H, 46.56(46.Sl) 559 5.43) 101411085)121111240) 76 11 10cm, 77 ll i-C3 1 711 l @0- CH3 42.514192 4.361393)116311222 14.141140) 79 1 C,1-1,, 443914444 4391453) 113211152)131411317) 30 11 1143.11, 46.70(46.70) 5.081506 104911089) 12.4711245)111 l i-C H, 46.99 5.06 10.22 12.22 a2 1 11-0 11. 49. 141413.71)56315.54) 9.1191 10.33) 117211181) 33 ll 14: 11.. 4727 5.96 9.44 11.13

TABLE lI-continued A Run Method Y R Analysis No. %C %H %N %S 84 11 J' 851 2-ethyl- 55.64( 55.0 7.271700 8.50(9.00] 991 1000 hexyl 86 11 0 C114060 4050 3.8l(3.80) 1144 1 [.81] 13.07( 13.50) 87 1 c 11, 4303(4302)4.39 438 10.7211 [.16] 1265(1275) 88 11 n-C H 4516 4528 50014.90 10041057 12. 12.08) 89 l i-C H, 45.15 4.87 9.89 12.01 90 11 on. 47.31)(5.38) (10.01 (11.47) 91 11 i-C H 47.15 5.59 9.88 11.41 I 92 11 2-c.11,,47.98 5.57 9.83 11.34

curs (temperature rose to 55C. The mixture is heated TABLE 1] to gentlereflux for three hours and then allowed to B cool. The white product isthen filtered off and washed P- Gas Evolution well with water. The driedproduct weighs 192.5g. This cc/g cclmmole h d .d d

is taken up in concentrated ammomum y rox1 e an 1 204 3- the solutionfiltered from insolubles, using Celite filter 3; {315% aid. The filtrateis acidified with dilute sulfuric acid and 43 -2 5 266 ll-2 the warmsuspension is filtered, washed well with wa- 44 209-21 1 154 68.7 o 4584486 240 1070 25 ter, and dried. Yield 164g. mp. 205 C (dec). 46198-199 186 71.5 47 172-175 179 73.4 48 170-171 163 71.5 49 ]90 19l 275205 Analysis. Cale. Found 50 157-158 199 92.7 %C 41 4 40 51 193-197 19978.8 H 394 395 52 30 N 12.23 11.89 53 187 3485 s 1397 13.94 54 197-198256 115.7 55 183-184 234 112.2 56 233 172 70.5 57 185-187 194 84.9 58129-130 176 82.0 EXAMPLE XXIV 59 193-196 237 110.4 35 2 3 33 3PREPARATION OF ETl-IYLENE BIS (3- 62 1 {3 11 P-TOLUENE SULFONYLCARBAZATE) 22 $12} $2; 282 In a manner similar to that described inExample 65 42-144 215 106.2 XXIII 186g (1.0 Mole) of p-toluene sulfonylhydrazide, 2f, gggjgg fig 40 92.4g sodium bicarbonate and 500 ml. ofwater are 68 170-171 164 76.4 stirred together as 93.5g (0.5. mole) ofethylene bis (dewmPJ chloroformate is added dropwise. The mixture warms70 160-162 204 100.8 0 71 265 ldecomp) 179 713 up to 40 C as carbondioxlde 1s evolved. The mixture s 72 5 n) 187 heated to refluxtemperature until no more CO 1s 32 5:; 23:23:13; $2; 321% 45 evolved.The product is cooled and filtered and washed 75 257 (decomp.) 166 85.9well with water. Yield 195g mp 235C (dec.) 76 207-208 160 78.1 77223-224 237 115.7 73 260 l wmp-l 136 Analysis Calc. Found 79 225(decomp.) 124 60.3 80 154.5 79.7 50 c 44.44 44.34 81 208-209 230 118.2 H4.52 4.51 82 210-211 143 77.5 N 11.52 11.38 83 191-192 137 74.3 8 13.1713.01 84 199-200 190 103.0

85 144-146 86 -181 166 78.7 87 -187 173 86.8 88 170-172 174 92.2 55EXAMPLE xxv 89 194-199 221 117.1 90 124-125 142 79.3 POLYMERJC REACTIONPRODUCT OF 4.4 g; 52:52; 5 {3-2 BlPI-IENYLENE BIS (SULFONYL HYDRAZIDE)AND ETHYLENE BIS (CHLOROFORMATE) 59 In a 2 liter 3 neck flast are placed17 lg (0.5 mole) of 4,4 biphenylene bis (sulfonyl hydrazide) 925g (1.1EXAMPLE xxm mole) NaHCO and 1000 ml. acetonitrile. The mix is Into a 2liter 3-necked flask is introduced 172g (1.0 heated to 50C and stirredas 935g (0.5. mole) ethylmole) of benzene sulfonyl hydrazide, 92.4g (1.1mold) ene bis(chlorof0rmate) is gradually added. Carbon diof sodiumbicarbonate and one liter of acetonitrile. The oxide is evolved. Afterthe addition of the chloroformixture is stirred as 93.5g (0.5 mole) ofethylene bis (chloroformate) is added gradually over one hour. Carbondioxide is evolved and an exothermic reaction ocmate is completed, themixture is heated to reflux until no more CO, is evolved. The mixture isthen cooled and the solid product filtered off (288g). The product(containing sodium chloride) is suspended in warm The specific gravityof the unblown resin 1.56 g/cc.

water and agitated. The solid is filtered off and washed well with warmwater and dried. Yield 229g. This EXAMPLE XXVI" ggg OF POLYES FER meltswith decomposition at 243 C.

The blowing agents listed below are tumple blended with the samepolyester resin of Example XXVI] using Analysis Cale Fmmd 22.7 g. ofblowing agent in 5 pounds (2265 g.) of resin C 42.10 41.05 and each mixis placed in the hopper of a 3 oz. recipro- H cating screw Ankerwerkinjection molding machine N 12.23 11.23 5 M03 [3.76 and the followingconditions are held constant during the injection of each mix (to formparts measuring 3 inch X 2.25 inch X 0.125).

EXAMPLE XXVI EXPANSION OF POLYVINYL CHLORIDE WllI-IISOPROPYL-3-(P-TOLUENE M SULFONYL) CARBAZATE Zone 1 250C Zone 2 250C APVC pipe compound of the followin g recipe is pre- Nozzle 293C paredStock 265-270C Pressure (PSI) parts PVC resin (sp. vise. .38 at .4%soln. in nitrobenzene at C.) 100 Tributyl tin mercaptoglycollate 2Calcium stearate 2 Sodium stearate 0.25 Petroleum wax (microcrystallinewith a m.p. of 143150C.) 0.8 Titanium dioxide 10 Poly(methylmethacrylate] (intrinsic visci 1.44 at 30 C in toluene) 4.0 lsopropyll-3-(p-toluene sulfonyhcarhazate 0.2

This composition is thoroughly mixed and [S then m- Irv-action 800troduced into a 2- /2 Davis standard extruder (with aux- 30 Back 200illiary cmpacter) equipped with a two stage screw (2/1 W compressionratio) and a l inch schedule die. The g g gil g following conditions areemployed in the extruder:

Barrel temperature The resultant extruded product is well expanded andQhibits a 5l3ecific gravity of as compafed to P Mold closed -this timewas varied for each blowing clfic fi "y of for unexpanded P- agent.Parts were obtained with the mold closed for blowing agent) sample ofthe same composition. 420 seconds EXAMPLE XXVI] EXPANSION OF POLYESTERThe fOHOWmg blowmg agents are tested- RESIN Wei ht of Tests on twosulfonyl carbazate compounds as blowing agents in are conducted in a 302 Van Dorn recipro- I) no blowing agent 21 g. cating screw in ectionmolding machine. The polyester (2) CBi h l bi lf l isopmpyl betweenresin contains polybutylene-terephthalate and (3) l l If [h I l4l5 st 1en 30% glass fibers and has a viscosity of 5.7 X 10 poise 3 2 5 yene on)e y at a shear rate 100 see 250C. The following concli- (4) ppg pfiflylenfl flsulfonyl isobutyl car azate) tions are used in both tests.[5) ppkBiphenylenebiswulfonyl Injection forward 3 sec. Booster time 1V2sec Clamp closed 60 sec. Barrel residence 15 sec. Injection pressure16001800 psi Back pressure 55 psi Screw speed RPM Temperatures C.Blowing Agent Amt. Rear Front Nozzle Stock Mold Sp. (3. 44'-Biphenylenebis(isopropylJ-sulfonyl carbazalel 05 235 246 277 260 381.14 g/cc 4 4'-Biphenylenebis( methyl- 3-sulfonyl carbazale) 0.5 235 246271 260 38 1,09 g/cc -continued Weight of part ethylhexyl carbazate)p,p-Biphenylenebis(sulfonyl n-butyl carbazate)l.3-Dimethylbenzene-4.6bis (sulfonyl methyl carbazate)p.p'-Oxybis(benzene sulfonyl ethyl carbazate) p,p'-O tybis(benzenesulfonyl isopropyl carbazate) p.p'-Biphenylenebis(sulfonyl methylcarbazate) The reduction in density from 21 g. for the unexpandedpolymer to values of 14-15 g. for each of the blowing agentsdemonstrates the expanding action of these agents.

EXAMPLE XXIX EXPANSION OF A RUBBER COMPOSITION WITH P,P-OXYBIS(N-BENZENESULFONYL-N'-CARBOISOPROPOXY I-IYDRAZIDE) A rubber composition of thefollowing recipe is prepared:

Masterbatch 50% Nitrile rubber/50% PVC by weight l00.0

Epoxidized soybean oil. 6.5%

oxiran content (wt) 4.0

Epoxidizcd soybean oil. 6.0%

oxiran content (wt) 8.0

Medium thermal carbon black 20.0

Phthalatc plasticizer. sp. grav.

Dioctyl phthalate 12.0

Antimony oxide 6.65

Diphenyl guanidine .33

Zinc diethyldithiocarbamate Spider sulfur 2.7

This masterbatch is then formulated as follows:

-cont1nued Temp. Time A B C D These data demonstrate the blowingproperties of p,p'-Oxybis(N-benzene sulfonyl-N-carboisopropoxyhydrazide). As can be seen, temperatures in the l80C. range aredesirable and urea or urea-zinc oxide combination provide effectiveactivation.

EXAMPLE XXX EXPANSION OF ETI-IYLENE-PROPYLENE RUBBER An ethylene (47.5%by weight)-propy1ene (47.5% ethylideneorbomene (5%) terpolymer (EPDM)having a Mooney viscosity of at 100C. is compounded in a Banbury-typeinternal mixer using the following reci- BBIH p,p'-biphenylencbis(3cnrboisopropoxy sulfonyl hydrazide) OBEl-l p.p'-dipl1enylctherbis(3-carboisopropoxy sulfonyl hydrazide) A B C D Masterbatch164.68 l64.68 164.68 164.68 p.pOxybis(Nbenzenesulfonyl-N'-carhoisopropoxy hydrazide) 2.0 2.0 2.0 20Zinc oxide 3.3 3.3 Surface treated urea L3 L3 l66.68 169.98 l67.98l7l.28

The materials of the masterbatch are blended on a 50 rubber millandother additives are subsequently blended in on the mill as indicated.The stocks are then extruded through a V4 inch round die and cut into 4inch lengths. The piecees were coated with talc and placed in a tray ina hot oven for a. 5, l0, l5, and 20 at l50C.

b. 5, l0, l5, and 20 at 165C.

c. 5, 10, I5, and 20' at l75C.

The density of the expanded pieces were measurued (lbs/cu. ft.)-seeTable I.

TABLE I Densities of Expanded Sponge Temp. Time A B C D 5' 64.4 69.150.6 4L4 10 58.2 61.4 36.3 35.8 l5(]C.

The following compounding procedure is used:

Banbury, No. 1 speed, no heating or cooling 0' charge EPDM 1' load boiland carbon black 3' load :Soil and CaCO 5' load boil and remainingingredients 7% dump masterbatch Time The above compounded stock wascured in an air oven for ID minutes at [C, and about 4 hours laterdensity measurements were taken with these results:

Density lbs/ft 40.8

23 This experiment indicates that a reduction of density of at least 35%was achieved employing the blowing agents of the invention in thisformulation.

EXAMPLE XXXI EXPANSION OF NlTRILE RUBBER'POLY(VlNYL CHLORIDE) BLEND Ablend of 70% (by weight) nitrile rubber(NBR)- 30% PVC, Mooney viscosity(ML-4) of 55 at lC. is compounded with the following ingredients in aBan- DlDA p.p'-Diphenylaminchist l,l,3,3-tetramcthylbutyl) Blilhl and"OBEH See Example XXX The above ingredients are compounded under thefollowing conditions:

Banbury, No. 1 Speed, no heating, no cooling 0' Load Blend l Load V DO?and carbon black 2% Load V4 DOP and CaCO 4 Load /4 DOP and remainingingredients 5% Load V4 DOP Time The above stocks are cured in an airoven for l0 minutes at 195C, and are then measured for density afterabout 4 hours with these results:

A B C Density. lbs/ft An effective reduction of density of at least 40%was achieved employing the blowing agents of the invention in thisformulation.

What is claimed is:

l. A composition comprising a gas-expandable polymeric material and atleast one sulfonyl carbazate containing at least one SO NHNHCOO--group.

2. The composition of claim 1 wherein the sulfonyl carbazate has theformula RSO,-NHNHCOOR' wherein R and R are the same or different and arealkyl having I to l2 carbon atoms, alkenyl having 2 to l2 carbon atoms,aryl, aralkyl, and alkaryl having 6 to 10 carbon atoms, and cycloalkylhaving 5 to 8 carbon atoms.

3. The composition of claim 2 wherein R is a secondary alkyl radicalhaving 3 to 8 carbon atoms.

4. The composition of claim 2 wherein R is isopropy 5. The compositionof claim 2 wherein R is secbutyl.

6. The composition of claim 1 wherein the sulfonyl carbazate has theformula ROOCNHNH-SO1Y4SO2NHN- HCOOR wherein the R substituents are thesame or different and are alkyl having l to 12 carbon atoms, alkenylhaving 2 to l2 carbon atoms, aryl. aralkyl, and alkaryl having 6 to lOcarbon atoms, and cycloalkyl having 5 to 8 carbon atoms: and

24 wherein Y is alkylene having 2 to 12 carbon atoms, arylene andalkarylene having 6 to 12 carbon atoms, and a group of the formula R -ZRwherein Z is a single bond connecting R'-' and R", O, S, SO. 50 NR"wherein R is hydrogen or an alkyl group with l to 4 carbon atoms,alkylene having 1 to 6 carbon atoms. and alkylidene having 2 to 3 carbonatoms. and wherein R and R are the same or different and are alkylenehaving 2 to 4 carbon atoms and phenylene.

7. The composition of claim 6 wherein the R substituents are the same.

8. The composition of claim 6 wherein the R substituents are secondaryalkyl radicals having 3 to 8 carbon atoms.

9. The composition of claim 6 wherein the R substituents are isopropylradicals.

10. The composition of claim 6 wherein the R sub stituents are sec-butylradicals.

11. The composition of claim 6 wherein Y is selected from alkylenehaving 2 to 4 carbon atoms.

12. The composition of claim 6 wherin Y is selected from the groupconsisting of phenylene. biphenylene, naphthalene, tolylene, xylylene,and oxybis (phenylene).

13. The composition of claim 6 wherein Z is O.

14. The composition of claim 1 wherein the sulfonyl carbazate has theformula.

wherein the R substituents are the same or different and are alkylhaving l to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms. aryl,aralkyl. and alkaryl having 6 to [0 carbon atoms, and cycloalkyl having5 to 8 carbon atoms; and wherein Y is alkylene having 2 to 12 carbonatoms, arylene and alkarylene having 6 to l2 carbon atoms, and a groupof the formula R=-Z- R=- wherein Z is a single bond connecting R and R,O, S, -S(), SO NR-- wherein R" is hydrogen or an alkyl group with l to 4carbon atoms. alkylene having 1 to 6 carbon atoms, and alkylidene having2 to 3 carbon atoms, and wherein R and R are the same or different andare alkylene having 2 to 4 carbon atoms and phenylene.

15. The composition of claim 14 wherein the R substituents are the same.

16. The composition of claim 14 wherein Z is -O-. 17. The composition ofclaim 1 wherein the sulfonyl carbazate is a polymer of the formula Y so,NHNH-Co0-Y'-0oC NHN- H so,+

wherein Y and Y are the same or different and are alkylene having 2 to12 carbon atoms, arylene and alkarylene having 6 to l2 carbon atoms, anda group of the formula -R2ZR= wherein Z is a single bond connecting Rand R, O, S, SO, SO NR wherein R is hydrogen or an alkyl group with l to4 carbon atoms, alkylene having 1 to 6 carbon atoms, and alkylidenehaving 2 to 3 carbon atoms. and wherein R and R are the same ordifferent and are alkylene having 2 to 4 carbon atoms and phenylene. andwherein n is 2 to 100.

18. The composition of claim 17 wherein n is 2 to S0.

l9. The composition of claim 17 wherein Y and Y are different.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. I 3,925,270

DATED 1 December 9, l975 |NVENTOR(S) BYRON A. HUNTER It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Claim 5, l ine l underl ine "sec".

Claim 6, the formula at lines 3 and l should read;

Claim l0, line 2, underllne sec".

Claim l2, l ine l delete "wherin and insert --wherein--.

Claim Hi, the formula at line 3 should read:

R-SO -NHNH-COO-Y' -OOC-NHNH-SO R Claim l7, the formula at line 3 shouldread:

Signed and Scaled this Arrest:

RUTH C. MASON C. MARSHA Arresting Officer LL DANN Commissioner ofPatemsand Trademarks

1. A COMPOSITION COMPRISING A GAS-EXPANDABLE POLYMERIC MATERIAL AND ATLEAST ONE SULFONYL CARBAZATE CONTAINING AT LEAST ONE -SO2-NHNH-COO-GROUP.
 2. The composition of claim 1 wherein the sulfonyl carbazate hasthe formula R-SO2-NHNH-COO-R1 wherein R and R1 are the same or differentand are alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbonatoms, aryl, aralkyl, and alkaryl having 6 to 10 carbon atoms, andcycloalkyl having 5 to 8 carbon atoms.
 3. The composition of claim 2wherein R1 is a secondary alkyl radical having 3 to 8 carbon atoms. 4.The composition of claim 2 wherein R1 is isopropyl.
 5. The compositionof claim 2 wherein R1 is sec-butyl.
 6. The composition of claim 1wherein the sulfonyl carbazate has the formulaR1-OOC-NHNH-SO2-Y-SO2-NHNH-COO-R1 wherein the R1 substituents are thesame or different and are alkyl having 1 to 12 carbon atoms, alkenylhaving 2 to 12 carbon atoms, aryl, aralkyl, and alkaryl having 6 to 10carbon atoms, and cycloalkyl having 5 to 8 carbon atoms; and wherein Yis alkylene having 2 to 12 carbon atoms, arylEne and alkarylene having 6to 12 carbon atoms, and a group of the formula -R2 -Z-R3- wherein Z is asingle bond connecting R2 and and R3, -O-, -S-, -SO-, SO2-, -NR4-wherein R4 is hydrogen or an alkyl group with 1 to 4 carbon atoms,alkylene having 1 to 6 carbon atoms, and alkylidene having 2 to 3 carbonatoms, and wherein R2 and R3 are the same or different anad are alkylenehaving 2 to 4 carbon atoms and phenylene.
 7. The composition of claim 6wherein the R1 substituents are the same.
 8. The composition of claim 6wherein the R1 substituents are secondary alkyl radicals having 3 to 8carbon atoms.
 9. The composition of claim 6 wherein the R1 substituentsare isopropyl radicals.
 10. The composition of claim 6 wherein the R1substituents are sec-butyl radicals.
 11. The composition of claim 6wherein Y is selected from alkylene having 2 to 4 carbon atoms.
 12. Thecomposition of claim 6 wherin Y is selected from the group consisting ofphenylene, biphenylene, naphthalene, tolylene, xylylene, and oxybis(phenylene).
 13. The composition of claim 6 wherein Z is -O-.
 14. Thecomposition of claim 1 wherein the sulfonyl carbazate has the formula.R-SO2-NHNH-COO-Y''-OOC-NHNH-SO2-R wherein the R substituents are thesame or different and are alkyl having 1 to 12 carbon atoms, alkenylhaving 2 to 12 carbon atoms, aryl, aralkyl, and alkaryl having 6 to 10carbon atoms, and cycloalkyl having 5 to 8 carbon atoms; and wherein Y''is alkylene having 2 to 12 carbon atoms, arylene and alkarylene having 6to 12 carbon atoms, and a group of the formula -R2-Z-R3-wherein Z is asingle bond connecting R2 and R3, -O-, -S-, -SO-, -SO2-, -NR4- whereinR4 is hydrogen or an alkyl group with 1 to 4 carbon atoms, alkylenehaving 1 to 6 carbon atoms, and alkylidene having 2 to 3 carbon atoms,and wherein R2 and R3 are the same or different and are alkylene having2 to 4 carbon atoms and phenylene.
 15. The composition of claim 14wherein the R substituents are the same.
 16. The composition of claim 14wherein Z is -O-.
 17. The composition of claim 1 wherein the sulfonylcarbazate is a polymer of the formula-Y-SO2-NHNH-COO-Y''-OOC-NHNH-SO2-wherein Y and Y'' are the same ordifferent and are alkylene having 2 to 12 carbon atoms, arylene andalkarylene having 6 to 12 carbon atoms, and a group of the formula-R2-Z-R3-wherein Z is a single bond connecting R2 and R3, -O-, -S-,-SO-, -SO2-, -NR4- wherein R4 is hydrogen or an alkyl group with 1 to 4carbon atoms, alkylene having 1 to 6 carbon atoms, and alkylidene having2 to 3 carbon atoms, and wherein R2 and R3 are the same or different andare alkylene having 2 to 4 carbon atoms and phenylene, and wherein n is2 to
 100. 18. The composition of claim 17 wherein n is 2 to
 50. 19. Thecomposition of claim 17 wherein Y and Y'' are different.